JPH05508036A - Combination of transition metal complex dopants and iridium dopants with nitrosyl ligands in silver halide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to the production of photographic silver halide grains. In particular, the present invention It relates to the incorporation of metal complexes during the production of silveride grains.

Background technology Silver halide grains are developable when exposed to actinic radiation such as electromagnetic radiation. It is known in the photographic field that it is useful for forming latent images of high quality. crystal Silver bromide, silver chloride, silver iodide and combinations of these metal halides may be used in has been widely used in photographic products.

Color negative film, transparency (transparent positive), and color photographic paper The properties of these materials, especially their sensitivity, are important in producing color photographic products for and improvements in fine particle properties have continued.

However, higher contrast, lower fog and over a wider exposure range There is a need for such materials that have improved reciprocity.

Re5earch Disclosure, December 1989, 308119. As shown in 5ections I-IV, pages 993-1000, gelatin A wide range of different dopers are available for addition to emulsions of silver halide grains and crystals. sensitizers, spectral sensitizers, and chemical sensitizers have been proposed. These materials are used to make emulsions. proposed for addition as a dopant during production or as a sensitizer after emulsion formation. It's been coming. However, using such materials to obtain better photographic performance There is a continuing need for improvements in

U.S. Pat. No. 4.933.272 to McDugle et al. coordination ligand ) and internally contain transition metals selected from Groups 5 to IO of the Periodic Table of the Elements. The formation of silver halide grains exhibiting a face-centered cubic crystal lattice is disclosed.

These complexes play an important role in modifying photographic performance.

In column 4 of U.S. Patent No. 4.806.462 to Yamashita et al. , Magnesium, Calcium, Barium, Aluminum, Strontium, Lute rheuthium, rhodium, lead, osmium, iridium, white Halogenated which can be doped with various metals including gold, cadmium, mercury and manganese The production of silver photographic materials is disclosed.

However, while maintaining reciprocity during exposure, , improved photos with sharper legs (higher contrast) at lower exposures There is a need for the product. Regarding color print materials with these characteristics, have special needs.

Disclosure of invention The object of the invention is to overcome the drawbacks of the prior art mentioned above.

A further object of the invention is to provide an improved photographic product.

Another object of the invention is to develop improved speed sensitivity with long exposures and low intensity exposures. Our goal is to provide photographic paper.

Another object of the invention is to provide a photographic paper with improved contrast. It's there.

These and other objects of the invention generally relate to iridium and nitrosyl ligands. Doped in combination with a transition metal complex (hereinafter referred to as "nitrosyl complex") having By providing a halide emulsion consisting of radiation-sensitive silver halide, achieved. The doping method distributes the nitrosyl complex uniformly throughout the particles. about the out of the particle. er 10% byvolume).

In a preferred embodiment, the nitrosyl complex is about 0.03 to about 36 moles I)I)b( Iridium is present in an amount of about 10 to about 350 moles pI) b) exists in The preferred amount selection is less dopant for larger particles. The amount of pigment required depends on the size of the emulsion grains.

Mode for carrying out the invention The present invention relates to conventional methods of producing silver halide emulsions and methods produced by these methods. It offers a number of advantages over silver halide grains.

The present invention provides an improved method of controlling photographic responses. This method is especially useful for long exposures. Gives improved contrast between. The present invention relates to the doped halogenated Provides improved speed sensitivity at low intensity exposures for photographic products using silver.

The present invention further provides that the iridium and nitrosyl complexes are used in the finishing of silver halide grains. It has the advantage of not interfering with other sensitizers or additives that may be present. child These and other advantages will become apparent from further consideration of the specific description below. It will be. Silver halide emulsions are prepared by techniques well known in the art. can be generated. Common techniques commonly used are single jet and This is called double jet precipitation. Any of these techniques can be used in the present invention. Ru. Furthermore, this method involves the use of a first vessel in which the growth is later carried out in a separate mixer or second vessel. This can be carried out by nucleating silver halide grains within the process. Such technology is known and the above-referenced Re5search Disclosure, 1989. December, 308119 5ections I~■Cited in the patent described in has been done. It is believed that the present invention can be practiced with all known techniques for emulsion preparation. It will be done.

All known silver halide grains can be used in the present invention and the precipitation method described above. child These are halide combinations of chlorine, bromine and iodine with silver. The present invention It is preferable to use it with silver chloride particles used in regular color print photographic paper. was found. Its use is when high contrast at low exposure is particularly important It is suitable for color printing on photographic paper, and the effects of nitrosyl complexes and iridium are significant. It turned out that something was wrong. However, the advantage of the present invention is that tabular particles grain), bromide and bromoiodide platelets or other types of bromoiodide particles. I think it exists in the black and white and color films used.

The amount of transition metal nitrosyl complex used can be contrasted in combination with iridium. It can be any amount that results in the desired increase in weight. Also the size of emulsion grains Depending somewhat, the amount of nitrosyl complex can range from about 0.03 to about 36 moles I of the silver chloride grains. ) I) b is appropriate.

The amount of iridium added can be any amount that results in the desired increase in low intensity speed sensitivity. It can be the amount. Large amounts of iridium shorten the time lapse between exposure and processing. , typically for an hour or less, resulting in deterioration of the latent image. iridium and nitrosyl complexes maintain high contrast at low intensity exposures. At the same time, it also reduces the deterioration of the latent image. This suitable amount is about 10 to about 350 moles. I) I) b is iridium. A preferred amount is about 36 moles I of the nitrosyl complex. ) about 70 moles of iridium for the preferred silver chloride grains when used in pbO amounts. It was found that it was Leppb.

The nitrosyl complex and iridium can be added at any suitable point in the emulsion manufacturing process. I can do it. Generally, nitrosyl complexes are used as dopants during the particle manufacturing process. It turns out that it is preferable to flush the water with water.

This is because it produces particles with desired properties.

On the other hand, by adding iridium late in the particle generation process, it is possible to It has been found that it is preferable to bond iridium. Final particle volume approx. When 90 to about 95% precipitation has occurred, iridium can be added to the emulsion preparation. during emulsion production, preferably from about 93% to about 95% of the grain volume. It has been found that the addition of the compound to the compound gives the desired binding effect. Iridium and nitrosyl complexes Processing is used for grains used in any layer of color photographic paper or other photographic products. But you can do it. This particle improves the performance of magenta, cyan or yellow. suitable for improving.

The transition metal nitrosyl complex and the iridium source form silver halide grains. It may be any substance contained in the particles when Cesium and osmiu is the preferred transition metal. Disclosed in U.S. Patent No. 4,933.272 Nitrosyl complex compounds can be used. Appropriate for the present invention are as follows: It is.

(O3 (No) CI 5) -2 (O3(No)Brs:l-” (OS (No) 1.)-” (O3(No)F5)-” [OS (No) CI 4 (T e CN)) -2CO3 (No) Br4 (OCN))-”(O3(No)1.(TeCN))-2 [OS (No) C 14 (S e CN)) “” (O3 (NO) B r, (S e CN) )-2(O3(No)1.(SeCN))-2(O3(No>C1,(CN )2) -2(O3(No)Br,(CN)=)-2(OS(No)I2(S CN),)-”(O3(No)CI!(SCN),)-”(O3(No)CI (CN), )-” (O3(No)Br(CN)4)-”[OS(No)I(SCN),)-” (O3(No)(CN)I)-” Preferred materials are Cs20s(No)C1 and Cs20s(No)CI.

I found that.

Iridium is iridium halide, alkali metal iridium halide, alkali Earth metal iridium halides and alkyl- and aryl-ammonium iris Dium halides, such as iridium chloride (■), iridium chloride (■), hex Potassium sachloroiridate (III), hexachloroiridate (IV) acid Potassium and ammonium hexachloroiridium(II[) or (IV)] It can be added as a halide salt or complex in trivalent or tetravalent state, such as. Illigi A preferred source of iridium chloride is iridium chloride complexed with potassium or as a tetrasalt. It was found that the sample was 1g of IrC1g.

After producing silver halide grains doped with iridium and nitrosyl complexes, The emulsion of grains was washed to remove excess salt, which was then combined with the Re5ea cited above. rch Disclosure 308119. It can be chemically and spectrally sensitized in any desired manner. After sensitization, this emulsion with all suitable couplers and/or coupler dispersants to form the desired color. Film or print photographic materials can be made. These are also black and white photographic It can be used for printing materials.

Example The following examples illustrate the production method of the present invention and the particles produced according to the present invention. and is not intended to be exhaustive.

Manufacture of emulsion Solution used for emulsion production 1.8-Dithiooctanediol 10.5mg Water 532.　0cc Solution B Silver nitrate 170.0g Water 467, 8cc Solution C Sodium chloride 58.0g Water 480.　0cc solution Sodium chloride 58.0g CS20S (No) C1s 2.4t, tg water 480.　0cc Solution E Sodium chloride 58.0g K, IrC]s 37.0t, tg Water 480.　0cc Solution 8 was placed in a reaction vessel and stirred at 46°C. In order to produce emulsion 1, silver po Solution B and solution C were simultaneously added at a constant flow rate while adjusting the tension to 1.5 pC1. added to. In preparing these emulsions, the flow rate is approximately 0.53 molar unless otherwise indicated. /minute. The emulsion was then washed to remove excess salt. Emulsion grains are cubic The edge length was 0384 μm.

Emulsion 2 was prepared by placing solution A in a reaction vessel and stirring at a temperature of 46°C. Ta. Solution B and solution solution were added simultaneously at a constant flow rate in an amount equal to 93% of the particle volume. Silver Potato The initial pressure was adjusted to 1.59C1. After 93% of the particle volume has been obtained, the remainder of the reaction Solution C was used in place of the solution. Wash the emulsion to remove excess salt did. The particles were cubic with an edge length of 0.391 μm.

After 93% of the particle volume is obtained, add solution C until 95.3% of the particle volume is obtained. Emulsion 3 was prepared in the same manner as Emulsion 1 except that Solution E was used. Then anti Solution E was replaced with solution C for the remainder of the reaction. Wash the emulsion to remove excess salt did. The particles were cubic with an edge length of 0.390 μm.

Emulsion 4 was prepared by placing solution A in a reaction container and stirring at 46°C.

Solution B and solution were added simultaneously at a constant flow rate until 93% of the particle volume was obtained. . Then place solution E in place of solution until 95.3% of the particle volume is obtained. Solution E was replaced for the remainder of the reaction when 95.3% of the particle volume was obtained. Instead, it was replaced with solution C. The silver potential was adjusted to 1°5 pC1. wash the emulsion The solution was washed to remove excess salt. The particles are cubic and the edge length is 0.383 μm. Met.

Coupler Y = N ~ [4-chloro-3-((4,5-dihydro-5-year-old xo-1- (2,4,6-1-lichlorophenyl)-IH-pyrazol-3-yl]ami ]-phenyl]-2-(3-(1,1-dimethylethyl)-4-hydroxyphenyl) [phenoxy]-tetradecanamide coupler X = 2- (2,4-bis(1,1- dimethylpropyl)phenoxy)-N-(3,5-dichloro-4-ethyl-2- Hydroxyphenyl)-butanamide Examples 1-8 Each of the above four emulsions was melted at 40°C. 35mg of sensitizing dye A in each emulsion and 5 mg of NaxStOs + 5 mg of KAuC1a were added. Next, this milk The mixture was aged at 65°C. Furthermore, APMT 290mg, KBr 1710mg and and 130 mg of stilbene compound D were added. Divide this emulsion into halves of the emulsion. Add 17.4 mg of dye C and 25.4 mg of dye B to the other half. Omg was added. this The emulsion was added to paper at 183 mg/m2 with cyanogenic coupler X at 448 mg/m2. Coated on a support. Gelatin overcoat 1076 mg as a protective layer /m2 was applied. Apply the application for 10 seconds and 5 minutes using a WR12 filter. 0.008- hours and processed at 35°C as described below.

Color development 45 seconds Bleach fixation (FeEDTA) 45 seconds Triethanolamine (99%) 11.0cc/IK, SO2 45% 0.5 cc/I KBr　O, 025g/l KCl 1.3g/l The volume was made up to 1 liter with water and the pH was adjusted to 10.12.

After treatment, the coatings were read with a reflection densitometer. The results of Examples 1 to 8 are shown in Table 1. Table 1 The data show that the nitrosyl complex or shorter exposure times give higher contrast. (emulsion 2), while the iridium dopant gives a lower constant value than the long low intensity exposure. (Emulsion 3). Dopan The combination (Example 4) is an improvement in variation for a sloppy foot and low intensity exposure. For both, it shows an improved position compared to the control.

Also, the reduction in value due to the time between exposure and processing or iridium-containing emulsions (emulsions 3) can be observed more in the present invention (emulsion 4).

Examples 9-16 Each of the above four emulsions was dissolved at 40°C. 35mg of sensitizing dye A in each emulsion and 28 mg of a gold sensitizer as disclosed in U.S. Patent No. 2.642.316. was added. This emulsion was then aged at 65°C.

Furthermore, 275 mg of APMT, 933 mg of KBr and 235 stilbene compound mg was added. Next, divide this emulsion and add 7.4 mg of dye C1 to half of the emulsion. Add dye B25 to the other half. Omg was added. This emulsion was used in Examples 1 to 8. It was applied and treated in such a way that it could be applied. These results are shown in Table 3, and again based on the present invention. This shows the improvements that can be made. Emulsions with dopant combinations are compatible with long low-intensity exposures. It has a low constant value with little variation. Contrast sharp feet or improved low Given either the intensity location, the present invention shows improvements in response either alone or both.

Examples 17-20 The above emulsion was melted at 40°C. Each emulsion contains 280 mg of sensitizing dye A and sodium thiosulfate. 6.8 mg of thorium and 4.2 mg of potassium chloroaurate were added. Next, this breast The mixture was aged at 65°C. Before applying the emulsion to the paper support, KBr 1145m g, 92 mg of APMTl and 6613 mg of KCl were added to this emulsion.

This emulsion was combined with dye-forming coupler Y at an Ag coating amount of 280 mg/m2. It was applied at a coating amount of 448 mg/m2. Seratin layer as in Examples 1-8 was coated on top of a layer of emulsion plus coupler for protection. Exposure and processing are Examples 1-8 It was the same as what was described for. The results are shown in Table This shows the advantages of the present invention in that both long and low-intensity exposures result in less drastic changes.

Examples 21-24 The above four emulsions were melted at 40°C. Each emulsion contains 333 mg of sensitizing dye A and rice. Added 20 mg of gold sensitizer as disclosed in National Patent No. 2.642.361 did. This emulsion was aged at 65°C. Before applying, APM7380mg1K 1320 mg of Br and 16613 mg of K were added to this emulsion. Coated, exposed and processed as in Examples 17-20. Results in table■ show. Again, sharp legs or dopants with less change with long low intensity exposures The advantages of the present invention are obvious.

Examples 25-27 Solution B and solution E were added simultaneously at a constant flow rate until 93% of the particle volume was obtained. Emulsion 5 was produced in the same manner as Emulsion 4 except for this. Then 95.3% of the particle volume Solution E was replaced with solution E until a solution was obtained.

Emulsions 3.4 and 5 were melted at 40°C. U.S. Patent No. 2.642.36 for each emulsion. 17.8 mg of gold sensitizer as disclosed in No. 1 was added.

This emulsion was aged at 65°C, and then 1306 mg of KBr and 020 mg of dye were added. was added. This emulsion was coated as described in Examples 1-8. Using these examples Exposures were 1/10 seconds and 100 seconds with a WR12 filter. Processing is example 1 It was similar to that described for ~8. The results are shown in Table ■.

The results in Table V again show that the combination of dopants gives a sharper toe emulsion. and changes due to low intensity exposure are maintained when compared to iridium-doped emulsions. Which indicates that. Also, the change or dopant due to the time between exposure and processing It is improved by the combination of

However, the preferred invention of Example 26 is such that the position of the dopant is as shown in Example 27. When inverted from .

The invention has been described in detail with particular reference to preferred embodiments thereof, and variations and modifications thereof. It is to be understood that the invention is valid within the spirit and scope of the invention.

Transition metal complex dopants and iris with nitrosyl ligands in silver halide Dium dopant combination summary The present invention generally relates to the combination of iridium and transition metal complexes having nitrosyl ligands. Provides halide emulsions consisting of combination-doped radiation-sensitive silver halides This is achieved by The method of doping has a nitrosyl ligand The transition metal complex is uniformly distributed throughout the particles, and the iridium is distributed around the outside of the particles. The side IO consists of being present in % by volume.

In a preferred embodiment, the transition metal complex having a nitrosyl ligand is about 0.03 Iridium is present in an amount of from about 10 to about 350 moles ppb. Exist in quantity.

international search report 1”□Aa□Na　”’US　92102201

Claims (22)

[Claims] 1. Doped with iridium and a combination of transition metal complexes with nitrosyl ligands A photographic silver halide emulsion comprising radiation-sensitive silver halide. 2. The transition metal complex having the nitrosyl ligand is about 0.03 to 36 mole ppb. An emulsion according to claim 1, wherein the emulsion is present in an amount of . 3. Claim 1, wherein said iridium is present in an amount from about 10 to about 350 moles ppb. Emulsion as described in section. 4. The milk of claim 1, wherein said iridium is present in about the outer 10% of said particles. agent. 5. The transition metal complex having the nitrosyl ligand is distributed uniformly throughout the particle. The emulsion according to claim 1, wherein the emulsion is applied to a cloth. 6. The emulsion according to claim 1, wherein said silver halide comprises silver chloride. 7. The transition metal complex having the nitrosyl ligand is about 0.03 to 36 mole ppb. is present in an amount of from about 10 to about 350 mole ppb of the silver halide. An emulsion according to claim 1, wherein the emulsion is present in an amount. 8. 8. The milk of claim 7, wherein said iridium is present in about the outer 10% of said particles. agent. 9. The transition metal complex having the nitrosyl ligand is distributed uniformly throughout the particle. 9. The emulsion according to claim 8, which is used in a fabric. 10. Uniformly distributed throughout gelatin and particles with nitrosyl ligands and a transition metal complex consisting of iridium present in about 10% by volume on the outer side of the particle. A photographic emulsion consisting of silver halide grains. 11. 11. The emulsion according to claim 10, wherein said silver halide comprises silver chloride. 12. Claim 1 wherein said iridium comprises from about 10 to about 350 ppb of said particles. Emulsion according to item 0. 13. The transition metal complex having the nitrosyl ligand is K2Os(NO)Cl5 or An emulsion according to claim 10, wherein is present as Cs2Os(NO)Cl5. 14. At least one layer of the photographic element is a transition metal complex having a nitrosyl ligand A photographic element consisting of silver halide grains doped with a combination of and iridium. 15. The transition metal complex having the nitrosyl ligand is about 0.03 to about 36 mole p 15. A photographic element as claimed in claim 14, wherein the element is present in an amount of pb. 16. Claim 1, wherein said iridium is present in an amount from about 10 to about 350 moles ppb. Photographic element according to item 14. 17. Claim 14, wherein said iridium is present in about the outer 10% of said particles. photo element. 18. The transition metal complex having the nitrosyl ligand is uniformly distributed throughout the particles. 15. The photographic element according to claim 14, wherein the photographic element is distributed. 19. Claim 14, wherein the transition metal complex comprises osmium and cesium. Photo element included. 20. Claim 10, wherein the transition metal complex comprises osmium and cesium. emulsion. 21. Claim 14 wherein said nitrosyl ligand comprises an osmium ligand. Emulsion as described. 22. Claim 10 wherein said nitrosyl ligand comprises an osmium ligand. Emulsion as described.